Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass, and transparent electroconductive film

ABSTRACT

The invention includes sintered products for transparent electroconductive films, which are formed into films in a stable and efficient manner through sputtering or the like, sputtering targets of the sintered products, and transparent electroconductive glass and films formed from the targets. The transparent electroconductive glass and films have good transparency, good electroconductivity and good workability into electrodes, and are therefore favorable to transparent electrodes in organic electroluminescent devices as realizing good hole injection efficiency therein. The sintered products contain constituent components of indium oxide, tin oxide and zinc oxide in specific atomic ratios of the metal atoms, and optionally contain specific metal oxides of ruthenium oxide, molybdenum oxide, vanadium oxide, etc.

TECHNICAL FIELD

The present invention relates to sintered metal oxides of great use asblanks for transparent electroconductive films for display devices andothers, to targets of the sintered products for forming transparentelectroconductive films, to transparent electroconductive materials, andto transparent electroconductive glass and films formed from thetargets.

BACKGROUND ART

Recently, various display devices such as liquid-crystal displays,electroluminescent displays, field emission displays and others havebeen introduced into office appliances and also control systems infactories. These devices all have a sandwich structure with a displaymember put between transparent electroconductive films.

For the transparent electroconductive films, much used is indiumoxide-tin oxide (hereinafter referred to as ITO) to give ITO films. TheITO films are highly transparent and have low electric resistance, and,in addition, they are well etched and their adhesiveness to substratesis good. As having such good properties, the ITO films are widely usedin the art. In general, the ITO films are formed in various methods ofsputtering, ion-plating, vapor deposition, etc.

Though having such good properties, however, there still remain someproblems to be solved with the ITO films when they are used, forexample, as transparent electrodes for liquid-crystal display devices.The problems with the ITO films include their surface accuracy, thetapering processability of electrodes made of them, and theirworkability into electrodes with junctions or contact points.

Specifically, ITO itself is a crystalline metal oxide, and its crystalgrains grow in the step of forming it into films. The growing crystalgrains deposit on the surface of the ITO film, thereby lowering thesurface accuracy of the film. In the step of etching the ITO film forforming an electrode, the intergranular boundaries in the film are firstetched, and the etched surface of the electrode shall be roughened.Therefore, it is difficult to etch the ITO film with accuracy. Further,in the step of tapering the ITO film electrode, the intergranularboundaries in the film are also first etched, and the ITO grains willoften remain in the etched area. In that condition, the ITO filmelectrode could not be well insulated from the counter electrode,thereby often causing display failure.

To solve the problem, a transparent electroconductive materialcomprising indium oxide and zinc oxide was proposed, for example, inJapanese Patent Laid-Open No. 234565/1994. Its workability intoelectrodes was improved without its transparency and electroconductivitybeing not sacrificed. However, the indium oxide-zinc oxide material hasa bulk resistance of from 2 to 5 mΩ·cm, and the electric power to beapplied thereto for forming it into films is limited. Therefore, theproblem with the material is that the productivity in forming it intofilms is low.

In an organic electroluminescent device having a film electrode of ITO,holes must be transferred from the ITO film a electrode into the lightemission layer or into the hole transporting layer. For this, it isdesirable that the work function of the electrode material and that ofthe organic compound for the light emission layer or the holetransporting layer are nearly on the same level and that the energy gapbetween the anode and the hole transporting layer is as small aspossible. To reduce the energy gap, the difference between the workfunction of the anode material and the ionization potential of theorganic compound for the hole transporting layer must be reduced.Various organic compounds have been proposed for hole-transportingsubstances usable for forming the hole transporting layer. Of those,aromatic amine compounds, especially triphenylamine derivatives havebeen known to have good capabilities. Triphenylamine, one oftriphenylamine derivatives, has an ionization potential of from 5.5 to5.6 electron volts. On the other hand, for transparent electroconductivefilms, well known is indium oxide-tin oxide (hereinafter referred to asITO) having high transparency and low electric resistance. The workfunction of ITO is 4.6 electron volts. Accordingly, there shall be arelatively large energy gap between the anode and the electrontransportation layer both of such ordinary materials.

In that situation, proposed was an organic, light-emitting thin-filmdevice having an organic compound layer between an anode and a cathode,for example, in Japanese Patent Laid-Open No. 63771/1997. In this, theanode is of a thin film of a metal oxide of which the work function islarger than that of ITO. However, the thin-film anode of such a metaloxide has a light transmittance of 10% when the metal oxide is rutheniumoxide, and 20% when it is vanadium oxide. To increase the lighttransmittance, proposed was a two-layered structure composed of an ITOfilm and an ultra-thin film of the metal oxide, the ultra-thin filmhaving a thickness of not larger than 300 angstroms. Even in this case,however, the light transmittance of the two-layered structure is still40 to 60% or so. Therefore, the two-layered structure is stillproblematic in that its transparency is not satisfactory for transparentelectrodes for display devices.

DISCLOSURE OF THE INVENTION

The present invention is to provide sintered metal oxides capable ofbeing formed into films in a stable and efficient manner throughsputtering or the like, targets of the sintered products, andtransparent electroconductive glass and films formed from the targets.The transparent electroconductive glass and films have goodtransparency, good electroconductivity and good workability intoelectrodes, and when they are formed into transparent electrodes andused in organic electroluminescent devices, the difference between theirwork function and the ionization potential of the hole-transportingsubstances in the devices is small and therefore the transparentelectrodes do not lower the light emission efficiency of the devices.

Having assiduously studied so as to solve the problems noted above, we,the present inventors have found that using sintered products ofcompounds, which comprise indium oxide, tin oxide and zinc oxide in aspecific ratio, as transparent electroconductive materials solves theproblems. On the basis of this finding, we have completed the presentinvention.

Specifically, the invention includes first to fourth aspects, which aresummarized as follows:

[I] First Aspect of the Invention

[1] A sintered product that comprises constituent components of indiumoxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75,

Sn/(In+Sn+Zn)=0.20 to 0.45,

Zn/(In+Sn+Zn)=0.03 to 0.30,

and contains a hexagonal layer compound of In₂O₃.(ZnO)m with mindicating an integer of from 2 to 20, and a spinel-structured compoundof Zn₂SnO₄.

[2] The sintered product of above [1], which has a specific resistanceof smaller than 2 mΩ·cm.

[3] A sintered product that comprises constituent components of indiumoxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75,

Sn/(In+Sn+Zn)=0.20 to 0.45,

Zn/(In+Sn+Zn)=0.03 to 0.30,

and from 0.5 to 10 atomic %, relative to the total of all metal atomstherein, of an oxide of a positive tetra-valent or higher poly-valentmetal, and contains a hexagonal layer compound of In₂O₃.(ZnO)m with mindicating an integer of from 2 to 20, and a spinel-structured compoundof Zn₂SnO₄.

[4] The sintered product of above [3], in which the oxide of a positivetetra-valent or higher poly-valent metal is ruthenium oxide, molybdenumoxide or vanadium oxide.

[5] A sputtering target for transparent electroconductive films, whichcomprises the sintered product of any of above [1] to [4].

[6] An electron-beaming target for transparent electroconductive films,which comprises the sintered product of any of above [1] to [4].

[7] An ion-plating target for transparent electroconductive films, whichcomprises the sintered product of any of above [1] to [4].

[8] Transparent electroconductive glass prepared by coating the surfaceof glass with an amorphous transparent electroconductive film thatcomprises constituent components of indium oxide, tin oxide and zincoxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75,

Sn/(In+Sn+Zn)=0.20 to 0.45,

Zn/(In+Sn+Zn)=0.03 to 0.30,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of an oxide of a positive tetra-valent or higherpoly-valent metal.

[9] The transparent electroconductive glass of above [8], in which theoxide of a positive tetra-valent or higher poly-valent metal isruthenium oxide, molybdenum oxide or vanadium oxide.

[10] The transparent electroconductive glass of above [8] or [9], whichhas a light transmittance of at least 75% and a specific resistance ofat most 5 mΩ·cm, and in which the transparent electroconductive film hasa work function of at least 5.45.

[11] A transparent electroconductive film prepared by coating thesurface of a transparent resin film with an amorphous transparentelectroconductive layer that comprises constituent components of indiumoxide, tin oxide and zinc oxide in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75,

Sn/(In+Sn+Zn)=0.20 to 0.45,

Zn/(In+Sn+Zn)=0.03 to 0.30,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of an oxide of a positive tetra-valent or higherpoly-valent metal.

[12] The transparent electroconductive film of above [11], in which theoxide of a positive tetra-valent or higher poly-valent metal isruthenium oxide, molybdenum oxide or vanadium oxide.

[13] The transparent electroconductive film of above [11] or [12], whichhas a light transmittance of at least 75% and a specific resistance ofat most 5 mΩ·cm, and in which the transparent electroconductive layerhas a work function of at least 5.45.

[II] Second Aspect of the Invention

[1] A sintered product of a composition that comprises indium oxide, orindium oxide and zinc oxide and/or tin oxide in the following atomicratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.00 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

[2] A sintered product of a composition that comprises indium oxide and.zinc oxide, or tin oxide in addition to the former two oxides in thefollowing atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.05 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

[3] A sintered product of a composition that comprises indium oxide,zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.05 to 0.20,

Sn/(In+Zn+Sn)=0.02 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

[4] A sputtering target comprising the sintered product of any of above[1] to [3].

[5] An electron-beaming target comprising the sintered product of any ofabove [1] to [3].

[6] An ion-plating target comprising the sintered product of any ofabove [1] to [3].

[7] Transparent electroconductive glass prepared by coating the surfaceof glass with a transparent electroconductive film of a composition thatcomprises indium oxide, zinc oxide and tin oxide in the following atomicratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.00 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

[8] The transparent electroconductive glass of above [7], which has alight transmittance of at least 75% and a specific resistance of at most5 mΩ·cm, and in which the transparent electroconductive film has a workfunction of at least 5.45 electron volts.

[9] A transparent electroconductive film prepared by coating the surfaceof a transparent resin film with a transparent electroconductive layerthat comprises indium oxide, zinc oxide and tin oxide in the followingatomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.00 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

[10] The transparent electroconductive film of above [9], which has alight transmittance of at least 75% and a specific resistance of at most5 mΩ·cm, and in which the transparent electroconductive layer has a workfunction of at least 5.45 electron volts.

[III] Third Aspect of the Invention

[1] A transparent electroconductive material of a composition thatcomprises one or more metal oxides selected from indium oxide, zincoxide and tin oxide and contains from 0.5 to 20 atomic %, relative tothe total of all metal atoms therein, of one or more metal oxidesselected from iridium oxide, rhenium oxide and palladium oxide.

[2] A transparent electroconductive material of a composition thatcomprises metal oxide(s) of indium oxide, zinc oxide and tin oxide inthe following atomic ratios:

In/(In+Zn+Sn)=0.00 to 1.00,

Zn/(In+Zn+Sn)=0.00 to 0.25,

Sn/(In+Zn+Sn)=0.00 to 1.00,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

[3] A transparent electroconductive material of a composition thatcomprises metal oxides of indium oxide, zinc oxide and tin oxide in thefollowing atomic ratios:

In/(In+Zn+Sn)=0.50 to 1.00,

Zn/(In+Zn+Sn)=0.05 to 0.25,

Sn/(In+Zn+Sn)=0.00 to 0.50,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

[4] A transparent electroconductive material of a composition thatcomprises metal oxides of indium oxide, zinc oxide and tin oxide in thefollowing atomic ratios:

In/(In+Zn+Sn)=0.75 to 0.95,

Zn/(In+Zn+Sn)=0.05 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

[5] A sintered product prepared by sintering the composition of any ofabove [1] to [4].

[6] A sputtering target comprising the sintered product of above [5].

[7] Transparent electroconductive glass prepared by coating the surfaceof glass with a transparent electroconductive film of a composition thatcomprises one or more metal oxides selected from indium oxide, zincoxide and tin oxide and contains from 0.5 to 20 atomic %, relative tothe total of all metal atoms therein, of one or more metal oxidesselected from iridium oxide, rhenium oxide and palladium oxide.

[8] The transparent electroconductive glass of above [7], which has alight transmittance of at least 70% and in which the transparentelectroconductive film has a work function of at least 5.4 electronvolts.

[9] A transparent electroconductive film prepared by coating the surfaceof a transparent resin film with a transparent electroconductive layerthat comprises one or more metal oxides selected from indium oxide, zincoxide and tin oxide and contains from 0.5 to 20 atomic %, relative tothe total of all metal atoms therein, of one or more metal oxidesselected from iridium oxide, rhenium oxide and palladium oxide.

[10] The transparent electroconductive film of above [9], which has alight transmittance of at least 70% and in which the transparentelectroconductive layer has a work function of at least 5.4 electronvolts.

[IV] Fourth Aspect of the Invention

[1] A transparent electroconductive material of a composition thatcomprises metal oxide(s) of tin oxide, indium oxide and zinc oxide inthe following atomic ratios:

Sn/(Sn+In+zn)=0.55 to 1.00,

In/(Sn+In+Zn)=0.00 to 0.45,

Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

[2] The transparent electroconductive material of above [1], in whichtin oxide, indium oxide and zinc oxide are in the following atomicratios:

Sn/(Sn+In+Zn)=0.55 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.40,

Zn/(Sn+In+Zn)=0.05 to 0.25.

[3] The transparent electroconductive material of above [1], in whichtin oxide, indium oxide and zinc oxide are in the following atomicratios:

Sn/(Sn+In+Zn)=0.55 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.40,

Zn/(Sn+In+Zn)=0.05 to 0.20.

[4] The transparent electroconductive material of above [1], in whichtin oxide, indium oxide and zinc oxide are in the following atomicratios:

Sn/(Sn+In+Zn)=0.60 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.35,

Zn/(Sn+In+Zn)=0.05 to 0.20.

[5] A sintered product prepared by sintering the composition of any ofabove [1] to [4] at a temperature of not lower than 1200° C.

[6] A sputtering target comprising the sintered product of above [5],which has a specific resistance of at most 10 mΩ·cm.

[7] Transparent electroconductive glass prepared by forming, on thesurface of a glass substrate, a transparent electroconductive film of acomposition that comprises metal oxide(s) of tin oxide, indium oxide andzinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 1.00,

In/(Sn+In+Zn)=0.00 to 0.45,

Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

[8] The transparent electroconductive glass of above [7], in which thetransparent electroconductive film has a light transmittance of at least70% and a work function of at least 5.4 electron volts.

[9] A transparent electroconductive film prepared by forming, on thesurface of a transparent resin film, a transparent electroconductivelayer of a composition that comprises metal oxide(s) of tin oxide,indium oxide and zinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 1.00,

In/(Sn+In+Zn)=0.00 to 0.45,

Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

[10] The transparent electroconductive film of above [9], in which thetransparent electroconductive layer has a light transmittance of atleast 70% and a work function of at least 5.4 electron volts.

BEST MODES OF CARRYING OUT THE INVENTION

Embodiments of the invention are described below.

[First Aspect of the Invention]

The sintered product of the invention is a transparent electroconductivematerial for forming transparent electroconductive films, and its basicconstituent components are indium oxide, tin oxide and zinc oxide.

In this, the constituent components are in the following atomic ratios:

In/(In+Sn+Zn)=0.50 to 0.75,

Sn/(In+Sn+Zn)=0.20 to 0.45,

Zn/(In+Sn+Zn)=0.03 to 0.30,

preferably,

In/(In+Sn+Zn)=0.60 to 0.75,

Sn/(In+Sn+Zn)=0.20 to 0.35,

Zn/(In+Sn+Zn)=0.05 to 0.20,

more preferably,

In/(In+Sn+Zn)=0.60 to 0.70,

Sn/(In+Sn+Zn)=0.25 to 0.35,

Zn/(In+Sn+Zn)=0.05 to 0.15.

In the invention, the composition of the constituent components, indiumoxide, tin oxide and zinc oxide is defined as above. This is becausewhen a mixture of indium oxide and zinc oxide is baked at lowtemperatures, the electroconductivity of the resulting sintered productis low. In the invention, the reduction in the electroconductivity ofthe sintered product is prevented. When the mixture of indium oxide andzinc oxide is baked at high temperatures, the resulting sintered productcould be a hexagonal layer compound with increased electroconductivity.In the mixture, however, it is difficult to convert zinc oxide entirelyinto a hexagonal layer compound, and the increase in theelectroconductivity of the sintered product is limited. Accordingly, inthe invention, zinc oxide that could not be converted into a hexagonallayer compound is reacted with tin oxide to form a spinel-structuredcompound, whereby the electroconductivity of the sintered product of thecomposition is increased and the sputtering stability of targets of thesintered product is ensured.

Regarding the blend ratio of these components, if the atomic ratio ofindium oxide is smaller than 0.50, the surface resistance of thetransparent electroconductive film to be obtained herein will be highand the heat resistance thereof will be low; but if larger than 0.75,the transparent electroconductive film will crystallize to lower itstransparency. If the atomic ratio of tin oxide is smaller than 0.20,forming the spinel-structured compound of zinc oxide and tin oxide willbe incomplete; but if larger than 0.45, the surface resistance of thetransparent electroconductive film will be high. If the atomic ratio ofzinc oxide is smaller than 0.03, the transparent electroconductive filmwill readily crystallize; but if larger than 0.30, the heat resistanceof the film will be low.

The sintered product comprises the constituent metal oxides of which thecomposition falls within the defined range as above, and contains ahexagonal layer compound of In₂O3.(ZnO)m with m indicating an integer offrom 2 to 20, and a spinel-structured compound of Zn₂SnO₄.

The sintered product of the invention that comprises the constituentcomponents as above has high electroconductivity as so mentionedhereinabove, and its specific resistance is lower than 2 mΩ·cm.Accordingly, when a target of the sintered product is sputtered to forma film in a sputtering device, the sputtering stability is good and theproductivity in producing the film product is good.

The sintered product that comprises the constituent components, indiumoxide, tin oxide and zinc oxide, and additionally contains from 0.5 to10 atomic %, relative to the total of all metal atoms therein, an oxideof a positive tetra-valent or higher poly-valent metal, especiallypreferably ruthenium oxide, molybdenum oxide or vanadium oxide has awork function falling between 5.45 and 5.70 electron volts, and its workfunction is nearly on the same level as the average work function, 5.6electron volts, of organic compounds for light-emitting substances orhole-transporting substances for organic electroluminescent devices.Accordingly, transparent electroconductive films formed by sputtering atarget of the sintered product shall have high hole injection efficiencywhen used in organic electroluminescent devices. In the sinteredproduct, the proportion of the oxide of a positive tetra-valent orhigher poly-valent metal preferably falls between 1 and 5 atomic % tothe total of all metal atoms.

For producing the sintered product of the invention, for example,employed is a method comprising uniformly mixing and grinding powders ofstarting metal oxides in a mixing and grinding machine, for example, ina wet ball or bead mill or ultrasonically, then granulating theresulting mixture, shaping the resulting granules into bodies of desiredform by pressing, and finally baking them into sintered products. Inthis, the raw material powders are preferably mixed and ground as fineas possible, but, in general, they are mixed and ground to have a meangrain size of not larger than 1 μm. In the baking step, the shapedbodies are baked generally at a temperature falling between 1,200 and1,500° C., but preferably between 1,250 and 1,480° C., for a period oftime generally falling between 10 and 72 hours, but preferably between24 and 48 hours. In this, the heating rate may fall between 1 and 50°C./min.

In the baking step, the baking temperature is preferably not lower than1,250° C. in order that indium oxide and zinc oxide in the resultingsintered product could form a hexagonal layer compound of the formulanoted above. The baking temperature shall be at lowest 1,000° C. inorder that zinc oxide and tin oxide could form a spinel-structuredcompound.

Where the three-component system of the metal oxides is combined with anoxide of a positive tetra-valent or higher poly-valent metal, such asruthenium oxide, molybdenum oxide or vanadium oxide in preparing thesintered product of the invention, a suitable amount of powder of theadditional metal oxide such as ruthenium oxide is added to the powdersof the starting, three-component system metal oxides, and baked in thesame manner as above. Also in this case, baking the shaped bodies iseffected under the condition under which the hexagonal layer compound ofindium oxide and zinc oxide and the spinel-structured compound of zincoxide and tin oxide could be formed in the resulting sintered product.

[II] Second Aspect of the Invention

The sintered product of the invention for forming transparentelectroconductive films is of a composition that comprises indium oxide,or indium oxide and zinc oxide and/or tin oxide in the following atomicratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.00 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

More preferably, the sintered product is of a composition that comprisesindium oxide and zinc oxide, or tin oxide in addition to the former twooxides in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.05 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

Most preferably, the sintered product is of a composition that comprisesindium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.80 to 1.00,

Zn/(In+Zn+Sn)=0.05 to 0.20,

Sn/(In+Zn+Sn)=0.02 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of a metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide.

For the sintered product of the invention, the composition of the basicconstituent components, indium oxide, tin oxide and zinc oxide, may beindium oxide alone, or a mixture of indium oxide and a small amount ofzinc oxide, or a mixture of indium oxide, a small amount of zinc oxideand a small amount of tin oxide, as in the above.

Regarding the blend ratio of the constituent components, if the atomicratio of indium oxide is smaller than 0.80, the surface resistance ofthe transparent electroconductive film to be obtained herein will behigh and-the heat resistance thereof will be low. If the atomic ratio ofzinc oxide is smaller than 0.05, the transparent electroconductive filmcould not be etched satisfactorily. In this case, a small amount ofwater or hydrogen may be added to the system where the sintered productis sputtered to form films, whereby the etchability of the films formedcould be improved. If the atomic ratio of zinc oxide is larger than0.20, the electroconductivity of the transparent electroconductive filmwill be low. If the atomic ratio of tin oxide is smaller than 0.02, theelectroconductivity of targets of the sintered product will be low; butif larger than 0.20, the surface resistance of the transparentelectroconductive film formed will be high.

The sintered product comprises the basic constituent component, indiumoxide alone, or indium oxide and zinc oxide and/or tin oxide, andcontains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, an additional metal oxide selected from ruthenium oxide,molybdenum oxide and vanadium oxide. If the additional metal oxidecontent is smaller than 0.5 atomic %, the work function of thetransparent electroconductive film to be obtained herein could not beincreased to a satisfactory level; but if larger than 10 atomic %, thetransparency of the film will be low. More preferably, the additionalmetal oxide content falls between 1 and 7 atomic %, even more preferablybetween 1 and 5 atomic %, relative to the total of all metal atoms inthe composition.

The transparent electroconductive film from the sintered product thatcomprises the basic components of indium oxide and others and containsat least one additional component of ruthenium oxide, molybdenum oxideand vanadium oxide could have an increased work function of, forexample, at least 5.45 electron volts when the proportion of theadditional components falls within the defined range. The work functionof the transparent electroconductive film is nearly on the same level asthe average ionization potential, 5.5 to 5.6 electron volts, of organiccompounds for light-emitting substances or hole-transporting substancesfor organic electroluminescent devices. Accordingly, when thetransparent electroconductive film is used as the anode in an organicelectroluminescent device, the energy gap in hole injection from theanode to the hole transportation layer or to the light-emitting layer inthe device could be reduced, and therefore the device could ensureincreased hole injection efficiency. As a result, the driving voltagefor the organic electroluminescent device could be lowered, heatgeneration that may be caused by the energy gap between the constituentlayers could be retarded in the device, and the device could ensurelong-term stable light emission.

For producing the sintered product of the invention, for example,employed is a method comprising blending powders of the starting metaloxides in a predetermined ratio, uniformly mixing and grinding the blendin a mixing and grinding machine, for example, in a wet ball or beadmill or ultrasonically, then granulating the resulting mixture, shapingthe resulting granules into bodies of desired form by pressing, andfinally baking them into sintered products. In this, the raw materialpowders are preferably mixed and ground as fine as possible, but, ingeneral, they are mixed and ground to have a mean grain size of notlarger than 1 μm. In the baking step, the shaped bodies are bakedgenerally at a temperature falling between 1,200 and 1,500° C., butpreferably between 1,250 and 1,480° C., for a period of time generallyfalling between 10 and 72 hours, but preferably between 24 and 48 hours.In this, the heating rate may fall between 1 and 50° C./min.

[III] Third Aspect of the Invention

The transparent electroconductive material of the invention is of acomposition that comprises one or more metal oxides selected from indiumoxide, zinc oxide and tin oxide and contains from 0.5 to 20 atomic %,relative to the total of all metal atoms therein, of one or more metaloxides selected from iridium oxide, rhenium oxide and palladium oxide.

The transparent electroconductive material with betterelectroconductivity is of a composition that comprises metal oxide(s) ofindium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.00 to 1.00,

Zn/(In+Zn+Sn)=0.00 to 0.25,

Sn/(In+Zn+Sn)=0.00 to 1.00,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

More preferably, the transparent electroconductive material is of acomposition that comprises metal oxides of indium oxide, zinc oxide andtin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.50 to 1.00,

Zn/(In+Zn+Sn)=0.05 to 0.25,

Sn/(In+Zn+Sn)=0.00 to 0.50,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

The transparent electroconductive material with much betterelectroconductivity is of a composition that comprises metal oxides ofindium oxide, zinc oxide and tin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.75 to 0.95,

Zn/(In+Zn+Sn)=0.05 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.20,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

Most preferably, the transparent electroconductive material is of acomposition that comprises metal oxides of indium oxide, zinc oxide andtin oxide in the following atomic ratios:

In/(In+Zn+Sn)=0.85 to 0.95,

Zn/(In+Zn+Sn)=0.07 to 0.20,

Sn/(In+Zn+Sn)=0.00 to 0.15,

and contains from 0.5 to 20 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from iridium oxide,rhenium oxide and palladium oxide.

For the transparent electroconductive material of the invention, thecomposition of the basic constituent components, indium oxide, zincoxide and tin oxide, or a mixture of these metal oxides may be indiumoxide, zinc oxide or tin oxide each alone, or a mixture of indium oxideand zinc oxide, or a mixture of indium oxide and tin oxide, or a mixtureof indium oxide, zinc oxide and tin oxide, as in the above.

Regarding the blend ratio of the constituent components, indium oxide isnot always needed herein. However, in order that the material could beformed into transparent electroconductive films with low surfaceresistance, it is desirable the atomic ratio of indium oxide is at least0.5. Zinc oxide is not always needed herein. However, in order that thematerial could be formed into transparent electroconductive films withimproved etchability, a small amount of zinc oxide is added to thecomposition for the material. For this, for example, the atomic ratio ofzinc oxide may be at least 0.05. If the etchability of the transparentelectroconductive films formed from the material is poor, a small amountof water or hydrogen may be added to the system where the sinteredproduct of the material is sputtered to form the films, whereby theetchability of the films formed could be improved. If the atomic ratioof zinc oxide is larger than 0.25, the durability of the transparentelectroconductive films will be low. Tin oxide is not always neededherein, but is preferably present in the material of the invention inorder that targets formed from the material are desired to have highelectroconductivity. However, when the transparent electroconductivefilms to be formed from the targets are desired to have low surfaceresistance, it is preferable that the atomic ratio of tin oxide is atmost 0.5 in the material.

In the material, the basic constituent components shall be combined withany one of iridium oxide, rhenium oxide and palladium oxide or with amixture of the metal oxides that may be in any desired ratio. Theproportion of the additional metal oxides to be in the material shallfall between 0.5 and 20 atomic % relative to the total of all metalatoms constituting the material that includes the additional metaloxides. It may be given by the following formulae, in terms of theatomic ratio of the metals:

Ir/(In+Zn+Sn+Ir)=0.005 to 0.20,

Re/(In+Zn+Sn+Re)=0.005 to 0.20,

Pd/(In+Zn+Sn+Pd)=0.005 to 0.20,

preferably,

Ir/(In+Zn+Sn+Ir)=0.01 to 0.10,

Re/(In+Zn+Sn+Re)=0.01 to 0.10,

Pd/(In+Zn+Sn+Pd)=0.01 to 0.10,

more preferably,

Ir/(In+Zn+Sn+Ir)=0.03 to 0.08,

Re/(In+Zn+Sn+Re)=0.03 to 0.08,

Pd/(In+Zn+Sn+Pd)=0.03 to 0.08.

If the proportion of the additional components of iridium oxide, rheniumoxide and palladium oxide is smaller than 0.5 atomic %, the workfunction of the transparent electroconductive film to be obtained hereincould not be increased to a satisfactory level; but if larger than 20atomic %, the transparency of the film will be low.

The metal oxide composition comprising the basic constituent componentsas above and containing from 0.5 to 20 atomic %, relative to the totalof all metal atoms therein, of iridium oxide, rhenium oxide andpalladium oxide may be sintered to give sputtering targets, and thetargets give transparent electroconductive films through sputtering. Thefilms could have a light transmittance of at least 70%, and a workfunction of at least 5.4 electron volts. The work function of the filmsis nearly on the same level as the average ionization potential, 5.5 to5.6 electron volts, of organic compounds for light-emitting substancesor hole-transporting substances for organic electroluminescent devices.Accordingly, when the transparent electroconductive film is used as theanode in an organic electroluminescent device, the energy gap in holeinjection from the anode to the hole transportation layer or to thelight-emitting layer in the device could be reduced, and therefore thedevice could ensure increased hole injection efficiency. As a result,the driving voltage for the organic electroluminescent device could belowered, heat generation that may be caused by the energy gap betweenthe constituent layers could be retarded in the device, and the devicecould ensure long-term stable light emission.

For producing the transparent electroconductive material of theinvention, for example, employed is a method comprising blending powdersof the starting metal oxides in a predetermined ratio, followed byuniformly mixing and grinding the resulting blend in a mixing andgrinding machine, for example, in a wet ball or bead mill orultrasonically. In this, the raw material powders are preferably mixedand ground as fine as possible, but, in general, they are mixed andground to have a mean grain size of not larger than 1 μm.

To obtain sintered products from the transparent electroconductivematerial, for example, the material is granulated, then the resultinggranules are shaped into bodies of desired form by pressing, and theshaped bodies are finally baked. In the baking step, the shaped bodiesare baked generally at a temperature falling between 1,200 and 1,500°C., but preferably between 1,250 and 1,480° C., for a period of timegenerally falling between 10 and 72 hours, but preferably between 24 and48 hours. In this, the heating rate may fall between 1 and 50° C./min.

[IV] Fourth Aspect of the Invention

The transparent electroconductive material of the invention is of acomposition that comprises metal oxide(s) of tin oxide, indium oxide andzinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 1.00,

In/(Sn+In+Zn)=0.00 to 0.45,

Zn/(Sn+In+Zn)=0.00 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

More preferably, the transparent electroconductive material is of acomposition that comprises metal oxides of tin oxide, indium oxide andzinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.60 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.35,

Zn/(Sn+In+Zn)=0.05 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms: therein, of one or more metal oxides selected from vanadiumoxide, molybdenum oxide and ruthenium oxide.

Even more preferably, the transparent electroconductive material is of acomposition that comprises metal oxides of tin oxide, indium oxide andzinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.40,

Zn/(Sn+In+Zn)=0.05 to 0.25,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

Still more preferably, the transparent electroconductive material is ofa composition that comprises metal oxides of tin oxide, indium oxide andzinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.55 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.40,

Zn/(Sn+In+Zn)=0.05 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

Most preferably, the transparent electroconductive material is of acomposition that comprises metal oxides of tin oxide, indium oxide andzinc oxide in the following atomic ratios:

Sn/(Sn+In+Zn)=0.60 to 0.95,

In/(Sn+In+Zn)=0.00 to 0.35,

Zn/(Sn+In+Zn)=0.05 to 0.20,

and contains from 0.5 to 10 atomic %, relative to the total of all metalatoms therein, of one or more metal oxides selected from vanadium oxide,molybdenum oxide and ruthenium oxide.

For the transparent electroconductive material of the invention, thecomposition of the basic constituent components, tin oxide, indium oxideand zinc oxide, or a mixture of these metal oxides may be tin oxide,indium oxide or zinc oxide each alone, or a mixture of tin oxide andindium oxide, or a mixture of tin oxide and zinc oxide, or a mixture oftin oxide, indium oxide and zinc oxide, as in the above.

Regarding the blend ratio of the basic constituent components, it isdesirable that the atomic ratio of tin oxide is at least 0.55 in orderthat the cost of the material could be reduced and that the materialcould be formed into transparent electroconductive films with good heatresistance. Indium oxide is not always needed herein. However, in orderthat the material could be formed into transparent electroconductivefilms with high electroconductivity, it is desirable the atomic ratio ofindium oxide is at most 0.45. If the atomic ratio of indium oxide islarger than 0.45, the costs for producing transparent electroconductivefilms from the material will increase. Zinc oxide is not always neededherein. However, in order that the material could be formed intotransparent electroconductive films with improved etchability, zincoxide may be added to the composition for the material. The atomic ratioof zinc oxide to be added to the composition is preferably at least0.05. In order to improve the wet heat resistance of the transparentelectroconductive films formed from the material, the atomic ratio ofzinc oxide to be in the material is preferably at most 0.25. If theetchability of the transparent electroconductive films formed from thematerial is poor, a small amount of water or hydrogen may be added tothe system where the sintered product of the material is sputtered toform the films, whereby the etchability of the films formed could beimproved.

In the material, the basic constituent components shall be combined withany one of vanadium oxide, molybdenum oxide and ruthenium oxide or witha mixture of the metal oxides that may be in any desired ratio. Theproportion of the additional metal oxides to be in the material shallfall between 0.5 and 10 atomic % relative to the total of all metalatoms constituting the material that includes the additional metaloxides. It may be given by the following formulae, in terms of theatomic ratio of the metals:

V/(In+Zn+Sn+V)=0.005 to 0.10,

Mo/(In+Zn+Sn+Mo)=0.005 to 0.10,

Ru/(In+Zn+Sn+Ru)=0.005 to 0.10,

preferably,

V/(In+Zn+Sn+V)=0.01 to 0.08,

Mo/(In+Zn+Sn+Mo)=0.01 to 0.08,

Ru/(In+Zn+Sn+Ru)=0.01 to 0.08,

more preferably,

V/(In+Zn+Sn+V)=0.02 to 0.05,

Mo/(In+Zn+Sn+Mo)=0.02 to 0.05,

Ru/(In+Zn+Sn+Ru)=0.02 to 0.05.

If the proportion of the additional component of any of vanadium oxide,molybdenum oxide or ruthenium oxide or their mixture is smaller than 0.5atomic %, the work function of the transparent electroconductive film tobe obtained herein could not be increased to a satisfactory level; butif larger than 10 atomic %, the transparency of the film will be low.

The metal oxide composition comprising the basic constituent componentsas above and containing from 0.5 to 10 atomic %, relative to the totalof all metal atoms therein, of vanadium oxide, molybdenum oxide orruthenium oxide may be sintered to give sputtering targets, and thetargets give transparent electroconductive films through sputtering. Thefilms could have a light transmittance of at least 70%, and a workfunction of at least 5.4 electron volts. The work function of the filmsis nearly on the same level as the average ionization potential, 5.5 to5.6 electron volts, of organic compounds for light-emitting substancesor hole-transporting substances for organic electroluminescent devices.Accordingly, when the transparent electroconductive film is used as theanode in an organic electroluminescent device, the energy gap in holeinjection from the anode to the hole transportation layer or to thelight-emitting layer in the device could be reduced, and therefore thedevice could ensure increased hole injection efficiency. As a result,the driving voltage for the organic electroluminescent device could belowered, heat generation that may be caused by the energy gap betweenthe constituent layers could be retarded in the device, and the devicecould ensure long-term stable light emission.

For producing the transparent electroconductive material of theinvention, for example, employed is a method comprising blending powdersof the starting metal oxides in a predetermined ratio, followed byuniformly mixing and grinding the resulting blend in a mixing andgrinding machine, for example, in a wet ball or bead mill orultrasonically. In this, the raw material powders are preferably mixedand ground as fine as possible, but, in general, they are mixed andground to have a mean grain size of not larger than 1 μm.

To obtain sintered products from the transparent electroconductivematerial, for example, the material is granulated, then the resultinggranules are shaped into bodies of desired form by pressing, and theshaped bodies are finally baked. In the baking step, the shaped bodiesare baked generally at a temperature falling between 1,200 and 1,500°C., but preferably between 1,250 and 1,480° C., for a period of timegenerally falling between 10 and 72 hours, but preferably between 24 and48 hours. In this, the heating rate may fall between 1 and 50° C./min.The sintered products formed under the condition could have a specificresistance of at most 10 mΩ·cm.

The sintered products thus obtained are machined into bodies fittable tosputtering units, and a fitting tool is attached to each body. In thatmanner, obtained are sputtering targets with good electroconductivitythat could be sputtered stably.

[V] Transparent Electroconductive Glass and Films of the First to FourthAspects of the Invention

The targets produced in the manner mentioned above may be sputtered toform films on transparent substrates. The transparent substrates may beany conventional one, including glass substrates, and synthetic resinfilms and sheets with high transparency. Preferred synthetic resins forthe films and sheets are polycarbonate resins, polymethyl methacrylateresins, polyester resins, polyether-sulfone resins, polyarylate resins,etc.

For sputtering the targets to form transparent electroconductive filmson transparent substrates, preferably used are magnetron sputteringunits. The sputtering condition in the unit where the films are formedis described. The plasma output may vary, depending on the surface areaof the target used and on the thickness of the transparentelectroconductive film to be formed, but, in general, it may fallbetween 0.3 and 4 W per cm² of the surface area of the target, and theperiod of time for which the target is sputtered to form the film mayfall between 5 and 120 minutes. Under the condition, the transparentelectroconductive films formed could have a desired thickness. Thethickness of the transparent electroconductive films shall vary,depending on the type the display devices in which they are sued, but,in general, it may fall between 200 and 6000 angstroms, preferablybetween 300 and 2000 angstroms.

The targets of the sintered products may also be used for forming filmsin electron-beaming units or ion-plating units. In these units, thetargets could be formed into transparent electroconductive films underthe same condition as above.

In the transparent electroconductive glass and films of the inventionthus produced in the manner as above, the transparent electroconductivelayer formed on a transparent substrate has high light transmittance andlow specific resistance. The transparent electroconductive layer is welletched to give a transparent electrode. Specifically, after it is etchedwith hydrochloric acid or oxalic acid, its cross section in the boundarybetween the etched part and the non-etched part has a smooth profile,and the etched part is clearly differentiated from the non-etched part.The etched layer forms an electrode line circuit having a uniform widthand a uniform thickness. Accordingly, the transparent electroconductivelayer in the transparent electroconductive glass and films of theinvention can be well etched in any ordinary manner to give goodtransparent electrodes. When a transparent electroconductive film withpoor processability into electrodes is etched to form an electrode, theelectric resistance of the circuit that comprises the resultingelectrode will partly increase or decrease, and, as the case may be, theinsulating area in the circuit will fail to prevent electric conductionand the circuit will break down. Contrary to this, the circuit thatcomprises the transparent electrode fabricated in the invention is freefrom the troubles.

In the first aspect of the invention, the transparent electroconductivelayer formed from the sintered product that comprises thethree-component metal oxides and containing an oxide of a positivetetra-valent or higher poly-valent metal has a high light transmittanceof at least 75% and are therefore highly transparent. In addition, Ithas a specific resistance of at most 5 mΩ·cm and a work function of atleast 5.45. With the layer, the transparent electroconductive glass andfilms of the invention are favorable to transparent electrodes fororganic electroluminescent devices. In this embodiment, if theproportion of the additional metal oxide with a positive tetra-valent orhigher poly-valent metal is too large, the electroconductivity of thelayer will be low. Therefore, when the layer is desired to have highelectroconductivity, it shall have a laminate structure comprising alower layer of the three-component metal oxides and an upper layer ofthe additional metal oxide with a positive tetra-valent or higherpoly-valent metal. Thus layered, the two shall be sintered. Thetwo-layered, transparent electroconductive layer could have higherelectroconductivity, and its work function could be nearly on the samelevel as that of organic compounds for organic electroluminescentdevices. The layer is favorably used as an electrode in organicelectroluminescent devices.

In the transparent electroconductive glass and films of the secondaspect of the invention thus produced in the manner as above, the metaloxide composition of the transparent a electroconductive layer is thesame as that of the sintered product used for forming the layer.Regarding its transparency, the transparent electroconductive layer hasa light transmittance of larger than 75% for light having a wavelengthof 500 nm. Regarding its electroconductivity, the layer has a specificresistance of at most 5 mΩ·cm. As mentioned hereinabove, the workfunction of the layer is at least 5.45 electron volts and is higher thanthat of ordinary ITO films.

In the transparent electroconductive glass and films of the third aspectof the invention thus produced in the manner as above, the metal oxidecomposition of the transparent electroconductive layer is the same asthat of the sintered product used for forming the layer. Regarding itstransparency, the transparent electroconductive layer has a lighttransmittance of larger than 70% for light having a wavelength of 500nm. Regarding its electroconductivity, the layer generally has aspecific resistance of at most 5 mΩ·cm. As mentioned hereinabove, thework function of the layer is higher than that of ordinary ITO films,and is at least 5.4 electron volts nearly on the same level as theionization potential of organic compounds for light-emitting layers orhole transportation layers in organic electroluminescent devices.

In the transparent electroconductive glass and films of the fourthaspect of the invention thus produced in the manner as above, the metaloxide composition of the transparent electroconductive layer is the sameas that of the sintered product used for forming the layer. Regardingits transparency, the transparent electroconductive layer has a lighttransmittance of larger than 70% for light having a wavelength of 500nm. As mentioned hereinabove, the work function of the layer is higherthan that of ordinary ITO films, and is at least 5.4 electron voltsnearly on the same level as the ionization potential of organiccompounds for light-emitting layers or hole transportation layers inorganic electroluminescent devices.

Accordingly, the transparent electroconductive glass and films of theinvention are favorably used as transparent electrodes in variousdisplay devices such as typically organic electroluminescent devices.

The invention is described in more detail with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention.

[First Aspect of the Invention]

EXAMPLE I-1

(1) Production of Sintered Discs

Raw material powders of indium oxide, tin oxide and zinc oxide were fedinto a wet ball mill in the following atomic ratios:

In/(In+Sn+Zn)=0.50

Sn/(In+Sn+Zn)=0.25,

Zn/(In+Sn+Zn)=0.25,

and mixed and ground therein for 72 hours. The resulting mixture wasgranulated, and then pressed into discs having a diameter of 4 inchesand a thickness of 5 mm. The discs were put into a baking furnace andbaked therein under pressure at 1400° C. for 36 hours.

The sintered discs had a density of 6.6 g/cm³ and a bulk resistance of0.95 mΩ·cm.

Through X-ray diffractiometric analysis for the crystallinity of thesintered discs, it was verified that crystals of indium oxide, crystalsof a hexagonal phyllo-compound of indium oxide and zinc oxiderepresented by In₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

The sintered product having been prepared in (1) was formed intosputtering targets having a diameter of 4 inches and a thickness of 5mm. The target was set in a DC magnetron sputtering unit, and sputteredonto a glass substrate set therein.

Regarding the sputtering condition, the atmosphere in the unit was argongas combined with a suitable amount of oxygen gas; the sputteringpressure was 3×10⁻¹ Pa; the ultimate vacuum degree was 5×10⁻⁴ Pa; thesubstrate temperature was 25° C.; the power applied was 100 W; the timefor film deposition was 14 minutes.

The transparent electroconductive film formed on the glass substrate hada thickness of 1,200 angstroms, and was amorphous. Its lighttransmittance for light having a wavelength of 500 nm was measured witha spectrophotometer, and was 79%. The specific resistance of the film,measured according to a 4-probe method, was 0.36 mΩ·cm, and theelectroconductivity of the film was high. The work function of the filmwas measured through UV photoelectron spectrometry.

(3) Evaluation of Processability of Transparent Electroconductive Film

The transparent electroconductive film formed on the glass substrate in(2) was coated with a resist, exposed via a mask with linear holestherethrough, and developed. With the patterned resist thereon, the filmwas etched with an aqueous solution of hydrochloric acid. In the filmthus etched, the boundary between the etched area and the non-etchedarea had a smooth inclined surface. The part of the film that had beencontacted with the etching solution was removed, and no film residueremained in the area where the film had been contacted with the etchingsolution.

The evaluation data are given in Table I-2.

EXAMPLE I-2

Transparent electroconductive glass was produced in the same manner asin Example I-1, except that the glass substrate was kept at 215° C.during the sputtering process (2).

The transparent electroconductive film formed on the glass substrate wasevaluated, and the data are given in Table I-2.

EXAMPLE I-3

A transparent electroconductive film was produced in the same manner asin Example I-1, except that a polycarbonate substrate having a thicknessof 0.1 mm was used as the transparent glass substrate in the step (1).

The transparent electroconductive film formed on the polycarbonatesubstrate was evaluated, and the data are given in Table I-2.

EXAMPLE I-4

(1) Production of Sintered Discs

sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide, tin oxide and zincoxide were mixed in the following atomic ratios:

In/(In+Sn+Zn)=0.50

Sn/(In+Sn+Zn)=0.45,

Zn/(In+Sn+Zn)=0.05.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of0.98 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, crystals of a hexagonalphyllo-compound of indium oxide and zinc oxide represented byIn₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

EXAMPLE I-5

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide, tin oxide and zincoxide were mixed in the following atomic ratios:

In/(In+Sn+Zn)=0.70

Sn/(In+Sn+Zn)=0.25,

Zn/(In+Sn+Zn)=0.05.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of0.87 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, crystals of a hexagonalphyllo-compound of indium oxide and zinc oxide represented byIn₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

EXAMPLE I-6

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide, tin oxide and zincoxide were mixed in the following atomic ratios:

In/(In+Sn+Zn)=0.60

Sn/(In+Sn+Zn)=0.30,

Zn/(In+Sn+Zn)=0.10.

The sintered discs had a density of 6.7 g/cm³ and a bulk resistance of0.82 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, crystals of a hexagonalphyllo-compound of indium oxide and zinc oxide represented byIn₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

EXAMPLE I-7

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide, tin oxide and zincoxide were mixed in the following atomic ratios:

In/(In+Sn+Zn)=0.60

Sn/(In+Sn+Zn)=0.30,

Zn/(In+Sn+Zn)=0.10,

and the resulting mixture was further mixed with powder of rutheniumoxide in the following ratio:

Ru/(In+Sn+Zn+Ru)=0.02.

The sintered discs had a density of 6.7 g/cm³ and a bulk resistance of0.80 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, crystals of a hexagonalphyllo-compound of indium oxide and zinc oxide represented byIn₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1. In Table I-1, Me in the column of themetal oxide composition indicates Ru (the same shall apply to Mo andothers to be mentioned hereinunder).

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

EXAMPLE I-8

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide, tin oxide and zincoxide were mixed in the following atomic ratios:

In/(In+Sn+Zn)=0.60

Sn/(In+Sn+Zn)=0.30,

Zn/(In+Sn+Zn)=0.10,

and the resulting mixture was further mixed with powder of molybdenumoxide in the following ratio:

Mo/(In+Sn+Zn+Mo)=0.02.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of0.94 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, crystals of a hexagonalphyllo-compound of indium oxide and zinc oxide represented byIn₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

EXAMPLE I-9

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide, tin oxide and zincoxide were mixed in the following atomic ratios:

In/(In+Sn+Zn)=0.60

Sn/(In+Sn+Zn)=0.30,

Zn/(In+Sn+Zn)=0.10,

and the resulting mixture was further mixed with powder of vanadiumoxide in the following ratio:

V/(In+Sn+Zn+V)=0.02.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of0.99 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, crystals of a hexagonalphyllo-compound of indium oxide and zinc oxide represented byIn₂O₃.(ZnO)m with m being 4, 5 and 7, and crystals of aspinel-structured compound of essentially Zn₂SnO₄ were formed in thesintered discs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

Comparative Example I-1

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide and zinc oxide weremixed in the following atomic ratios:

In/(In+Zn)=0.85

Zn/(In+Zn)=0.15.

The sintered discs had a density of 6.75 g/cm³ and a bulk resistance of2.74 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide, and crystals of a hexagonalphyllo-compound of indium oxide-zinc oxide were formed in the sintereddiscs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

Since the specific resistance of the sintered discs used herein washigh, the sputtering stability thereof was poor. Therefore, it took 17minutes to form the film having the predetermined thickness.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

Comparative Example I-2

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in Example I-1. Inthis, however, raw material powders of indium oxide and tin oxide weremixed in the following atomic ratios:

In/(In+Sn)=0.90

Sn/(In+Sn)=0.10.

The sintered discs had a density of 6.71 g/cm³ and a bulk resistance of0.69 mΩ·cm. Regarding the crystallinity of the sintered discs, it wasverified that crystals of indium oxide were formed in the sintereddiscs.

The data are given in Table I-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example I-1. In this, however, the sintered discsprepared in the previous step (1) were used.

(3) Evaluation of Processability of Transparent Electroconductive Film

The processability of the transparent electroconductive film formed onthe glass substrate in the previous step (2) was evaluated in the samemanner as in the step (3) in Example I-1.

The evaluation data are given in Table I-2.

Comparative Example I-3

Transparent electroconductive glass was produced in the same manner asin Comparative Example I-2. In this, however, the temperature of theglass substrate in the sputtering step was 215° C.

The transparent electroconductive film formed on the glass substrate wasevaluated, and the evaluation data are given in Table I-2.

TABLE I-1 Example I-1 I-4 I-5 I-6 In/(In + Sn + Zn) 0.50 0.50 0.70 0.60Sn/(In + Sn + Zn) 0.25 0.45 0.25 0.30 Zn/(In + Sn + Zn) 0.25 0.05 0.050.10 Density of sintered discs (g/cm³) 6.6 6.8 6.8 6.7 Bulk resistance(mΩ · cm) 0.95 0.98 0.87 0.82 Crystallinity Indium oxide yes yes yes yesHexagonal phyllo- yes yes yes yes compound Spinel compound yes yes yesyes Comparative Example Example I-7 I-8 I-9 I-1 I-2 In/(In + Sn + Zn)0.60 0.60 0.60 0.85 0.90 Sn/(In + Sn + Zn) 0.30 0.30 0.30 — 0.10Zn/(In + Sn + Zn) 0.10 0.10 0.10 0.15 — Me/(In + Sn + Zn + Me) 0.02 0.020.02 — — Density of sintered discs (g/cm³) 6.7 6.8 6.8 6.75 6.71 Bulkresistance (mΩ · cm) 0.80 0.94 0.99 2.74 0.69 Crystallinity Indium oxideyes yes yes yes yes Hexagonal phyllo- yes yes yes no no compound Spinelcompound yes yes yes no no

TABLE I-2 Processability Specific into Electrodes Resistance of FilmLight (cross section of (mΩ · cm) Transmittance (%) Crystallinity WorkFunction (eV) etched film) Example I-1 0.36 79 amorphous 5.11 flat I-20.34 79 amorphous 5.12 flat I-3 0.37 78 amorphous 5.12 flat I-4 0.24 80amorphous 5.16 flat I-5 0.27 81 amorphous 5.18 flat I-6 0.29 80amorphous 5.15 flat I-7 1.3 79 amorphous 5.49 flat I-8 3.5 78 amorphous5.55 flat I-9 2.4 78 amorphous 5.57 flat Comparative Example I-1 0.34 80amorphous 5.18 flat I-2 0.42 80 microcrystalline 4.97 rough I-3 0.18 82crystalline 4.95 rough

[Second Aspect of the Invention]

EXAMPLE II-1

(1) Production of Sintered Discs

Raw material powders of indium oxide and ruthenium oxide were mixed inthe following atomic ratio:

Ru/(In+Ru)=0.03,

and the mixture was fed into a wet ball, and further mixed and groundtherein for 72 hours. The resulting mixture was granulated, and thenpressed into discs having a diameter of 4 inches and a thickness of 5mm. The discs were put into a baking furnace and baked therein underpressure at 1400° C. for 36 hours.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of0.80 mΩ·cm.

The data are given in Table II-1.

(2) Production of Transparent Electroconductive Glass

The sintered product having been prepared in (1) was formed intosputtering targets having a diameter of 4 inches and a thickness of 5mm. The target was set in a DC magnetron sputtering unit, and sputteredonto a glass substrate set therein.

Regarding the sputtering -condition, the atmosphere in the unit wasargon gas combined with a suitable amount of oxygen gas; the sputteringpressure was 3×10⁻¹ Pa; the ultimate vacuum degree was 5×10⁻⁴ Pa; thesubstrate temperature was 25° C.; the power applied was 100 W; the timefor film deposition was 14 minutes.

The transparent electroconductive film formed on the glass substrate hada thickness of 1,200 angstroms, and was amorphous. Its lighttransmittance for light having a wavelength of 500 nm was measured witha spectrophotometer, and was 79%. The specific resistance of the film,measured according to a 4-probe method, was 0.84 mΩ·cm, and theelectroconductivity of the film was high. The work function of the filmwas measured through UV photoelectron spectrometry, and was 5.51electron volts.

The evaluation data of the transparent electroconductive film are givenin Table II-2.

EXAMPLE II-2

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, molybdenum oxide was used in place ofruthenium oxide, and its atomic ratio was:

Mo/(In+Mo)=0.07.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-3

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, vanadium oxide was used in place ofruthenium oxide, and its atomic ratio was:

V/(In+V)=0.05.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-4

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andzinc oxide were mixed in the following atomic ratios:

In/(In+Zn)=0.83

Zn/(In+Zn)=0.17,

and the resulting mixture was further mixed with ruthenium oxide in thefollowing atomic ratio:

Ru/(In+Zn+Ru)=0.020.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-5

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andzinc oxide were mixed in the following atomic ratios:

In/(In+Zn)=0.85

Zn/(In+Zn)=0.15,

and the resulting mixture was further mixed with molybdenum oxide in thefollowing atomic ratio:

Mo/(In+Zn+Mo)=0.020.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-6

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andzinc oxide were mixed in the following atomic ratios:

In/(In+Zn)=0.85

Zn/(In+Zn)=0.15,

and the resulting mixture was further mixed with vanadium oxide in thefollowing atomic ratio:

V/(In+Zn+V)=0.020.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-7

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andzinc oxide were mixed in the following atomic ratios:

In/(In+Zn)=0.93

Zn/(In+Zn)=0.07,

and the resulting mixture was further mixed with ruthenium oxide in thefollowing atomic ratio:

Ru/(In+Zn+Ru)=0.015.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-8

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andzinc oxide were mixed in the following atomic ratios:

In/(In+Zn)=0.90

Zn/(In+Zn)=0.10,

and the resulting mixture was further mixed with molybdenum oxide in thefollowing atomic ratio:

Mo/(In+Zn+Mo)=0.050.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-9

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andzinc oxide were mixed in the following atomic ratios:

In/(In+Zn)=0.90

Zn/(In+Zn)=0.10,

and the resulting mixture was further mixed with vanadium oxide in thefollowing atomic ratio:

V/(In+Zn+V)=0.070.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-10

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andtin oxide were mixed in the following atomic ratios:

In/(In+Sn)=0.80

Sn/(In+Sn)=0.20,

and the resulting mixture was further mixed with ruthenium oxide in thefollowing atomic ratio:

Ru/(In+Sn+Ru)=0.030.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-11

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andtin oxide were mixed in the following atomic ratios:

In/(In+Sn)=0.80

Sn/(In+Sn)=0.20,

and the resulting mixture was further mixed with molybdenum oxide in thefollowing atomic ratio:

Mo/(In+Sn+Mo)=0.070.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-12

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andtin oxide were mixed in the following atomic ratios:

In/(In+Sn)=0.80

Sn/(In+Sn)=0.20,

and the resulting mixture was further mixed with vanadium oxide in thefollowing atomic ratio:

V/(In+Sn+V)=0.050.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-13

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andtin oxide were mixed in the following atomic ratios:

In/(In+Sn)=0.90

Sn/(In+Sn)=0.10,

and the resulting mixture was further mixed with ruthenium oxide in thefollowing atomic ratio:

Ru/(In+Sn+Ru)=0.021.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-14

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andtin oxide were mixed in the following atomic ratios:

In/(In+Sn)=0.90

Sn/(In+Sn)=0.10,

and the resulting mixture was further mixed with molybdenum oxide in thefollowing atomic ratio:

Mo/(In+Sn+Mo)=0.020.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-15

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide andtin oxide were mixed in the following atomic ratios:

In/(In+Sn)=0.90

Sn/(In+Sn)=0.10,

and the resulting mixture was further mixed with vanadium oxide in thefollowing atomic ratio:

V/(In+Sn+V)=0.020.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-16

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide,zinc oxide and tin oxide were mixed in the following atomic ratios:

In/(In+Zn+Sn)=0.80

Zn/(In+Zn+Sn)=0.10

Sn/(In+Zn+Sn)=0.10,

and the resulting mixture was further mixed with ruthenium oxide in thefollowing atomic ratio:

Ru/(In+Zn+Sn+Ru)=0.022.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-17

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide,zinc oxide and tin oxide were mixed in the following atomic ratios:

In/(In+Zn+Sn)=0.80

Zn/(In+Zn+Sn)=0.10

Sn/(In+Zn+Sn)=0.10,

and the resulting mixture was further mixed with molybdenum oxide in thefollowing atomic ratio:

Mo/(In+Zn+Sn+Mo)=0.050.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-18

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide,zinc oxide and tin oxide were mixed in the following atomic ratios:

In/(In+Zn+Sn)=0.80

Zn/(In+Zn+Sn)=0.10

Sn/(In+Zn+Sn)=0.10,

and the resulting mixture was further mixed with vanadium oxide in thefollowing atomic ratio:

V/(In+Zn+Sn+V)=0.050.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production Of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-19

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide,zinc oxide and tin oxide were mixed in the following atomic ratios:

In/(In+Zn+Sn)=0.90

Zn/(In+Zn+Sn)=0.07

Sn/(In+Zn+Sn)=0.03,

and the resulting mixture was further mixed with ruthenium oxide in thefollowing atomic ratio:

Ru/(In+Z h +Sn+Ru)=0.025.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the Sintered Discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-20

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide,zinc oxide and tin oxide were mixed in the following atomic ratios:

In/(In+Zn+Sn)=0.90

Zn/(In+Zn+Sn)=0.07

Sn/(In+Zn+Sn)=0.03,

and the resulting mixture was further mixed with molybdenum oxide in thefollowing atomic ratio:

Mo/(In+Zn+Sn+Mo)=0.035.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-21

(1) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (1) inExample II-1. In this, however, raw material powders of indium oxide,zinc oxide and tin oxide were mixed in the following atomic ratios:

In/(In+Zn+Sn)=0.90

Zn/(In+Zn+Sn)=0.07

Sn/(In+Zn+Sn)=0.03,

and the resulting mixture was further mixed with vanadium oxide in thefollowing atomic ratio:

V/(In+Zn+Sn+V)=0.035.

The physical properties of the sintered discs produced herein are givenin Table II-1.

(2) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (2) in Example II-1. In this, however, the sintered discsprepared in the previous step (1) were used. The transparentelectroconductive film formed on the glass substrate was evaluated, andthe data of its physical properties are given in Table II-2.

EXAMPLE II-22

Using a sintered disc that had been prepared in the same manner as inthe step (1) in Example II-4, as the target, transparentelectroconductive glass was produced in the same manner as in ExampleII-4. In this, however, the glass substrate was kept heated at 215° C.in the sputtering step (2).

The transparent electroconductive film formed on the glass substrate wasevaluated in the same manner as in the step

(2) in Example II-1, and the data are given in Table II-2.

EXAMPLE II-23

Using a sintered disc that had been prepared in the same manner as inthe step (1) in Example II-10, as the target, transparentelectroconductive glass was produced in the same manner as in ExampleII-10. In this, however, the glass substrate was kept heated at 215° C.in the sputtering step (2).

The transparent electroconductive film formed on the glass substrate wasevaluated in the same manner as in the step (2) in Example II-1, and thedata are given in Table II-2.

EXAMPLE II-24

Using a sintered disc that had been prepared in the same manner as inthe step (1) in Example II-10, as the target, transparentelectroconductive glass was produced in the same manner as in ExampleII-10. In this, however, 2% by weight of water was added to thesputtering system in the step (2).

The transparent electroconductive film formed on the glass substrate wasevaluated in the same manner as in the step (2) in Example II-1, and thedata are given in Table II-2.

The transparent electroconductive film thus produced herein was annealedat 215° C. for 1 hour, and its physical properties were measured. Beforeand after the annealing, there was found no chance in the physicalproperties of the film.

EXAMPLE II-25

Using a sintered disc that had been prepared in the same manner as inthe step (1) in Example II-4, as the target, a transparentelectroconductive film was produced in the same manner as in ExampleII-4. In this, however, a transparent polycarbonate substrate having athickness of 0.1 mm was used in place of the glass substrate used in thestep (2) in Example II-4.

The transparent electroconductive film formed on the polycarbonatesubstrate was evaluated in the same manner as in the step (2) in ExampleII-1, and the data are given in Table II-2.

Comparative Example II-1

A transparent electroconductive film was formed on a glass substrate inthe same manner as in the step (2) in Example II-1. In this, however,the target used was produced from a sintered product that had beenprepared in the same manner as in the step (1) in Example II-1 exceptthat a mixture of powders of indium oxide and tin oxide in the followingatomic ratios:

In/(In+Zn)=0.85

Zn/(In+Zn)=0.15,

was used alone without adding thereto any additional component ofruthenium oxide or the like.

The transparent electroconductive film formed on the glass substrate wasevaluated, and the evaluation data are given in Table II-2.

Comparative Example II-2

Sintered discs were produced in the same manner as in the step (1) inExample II-1, except that a mixture of powders of indium oxide and tinoxide in the following atomic ratios:

In/(In+Zn)=0.90

Zn/(In+Zn)=0.10,

was used alone without adding thereto any additional component ofruthenium oxide or the like. These were formed into sputtering targets.Using the target produced herein, transparent electroconductive glasswas produced in the same manner as in the step (2) in Example II-1. Inthis, however, the glass substrate was kept heated at 215° C. in thesputtering step.

The transparent electroconductive film formed on the glass substrate wasevaluated, and the evaluation data are given in Table II-2.

TABLE II-1 II-1 II-2 II-3 II-4 II-5 II-6 II-7 In/(In + Zn + Sn) 1.001.00 1.00 0.83 0.85 0.85 0.93 Zn/(In + Zn + Sn) — — — 0.17 0.15 0.150.07 Sn/(In + Zn + Sn) — — — — — — — Ru/(In + Zn + Sn + 0.030 — — 0.020— — 0.015 Ru) Mo/(In + Zn + Sn + — 0.070 — — 0.020 — — Mo) V/(In + Zn +Sn + V) — — 0.050 — — 0.020 — Density of Sintered 6.81 6.78 6.76 6.816.90 6.70 6.75 Discs (g/cm³) Bulk Resistance 0.80 0.88 0.95 0.95 2.741.72 0.95 (mΩ · cm) Example II-8 II-9 II-10 II-11 II-12 II-13 II-14In/(In + Zn + Sn) 0.90 0.90 0.80 0.80 0.80 0.90 0.90 Zn/(In + Zn + Sn)0.10 0.10 — — — — — Sn/(In + Zn + Sn) — — 0.20 0.20 0.20 0.20 0.10Ru/(In + Zn + Sn + — — 0.030 — — 0.021 — Ru) Mo/(In + Zn + Sn + 0.050 —— 0.070 — — 0.020 Mo) V/(In + Zn + Sn + V) — 0.070 — — 0.050 — — Densityof Sintered 6.85 6.68 6.72 6.76 6.56 6.81 6.95 Discs (g/cm³) BulkResistance 1.85 4.85 0.74 0.92 1.92 0.79 0.93 (mΩ · cm) Example II-15II-16 II-17 II-18 II-19 II-20 II-21 In/(In + Zn + Sn) 0.90 0.80 0.800.80 0.90 0.90 0.90 Zn/(In + Zn + Sn) — 0.10 0.10 0.10 0.07 0.07 0.07Sn/(In + Zn + Sn) 0.10 0.10 0.10 0.10 0.03 0.03 0.03 Ru/(In + Zn + Sn +— 0.022 — — 0.025 — — Ru) Mo/(In + Zn + Sn + — — 0.050 — — 0.035 — Mo)V/(In + Zn + Sn + V) 0.020 — — 0.050 — — 0.035 Density of Sintered 6.556.74 6.78 6.57 6.71 6.78 6.58 Discs (g/cm³) Bulk Resistance 1.93 0.921.85 1.85 0.98 1.98 1.98 (mΩ · cm)

TABLE II-2 Specific Resistance of Light Transmittance Film (mΩ · cm) (%)Crystallinity Work Function (eV) Example II-1  0.84 79 microcrystalline5.51 II-2  1.51 80 rnicrocrystalline 5.48 II-3  4.10 79 microcrystalline5.49 II-4  1.70 79 amorphous 5.52 II-5  2.80 76 amorphous 5.46 II-6 3.70 79 amorphous 5.47 II-7  1.20 79 amorphous 5.45 II-8  2.10 77amorphous 5.49 II-9  3.12 80 arnorphous 5.50 II-10 0.70 81microcrystalline 5.52 II-11 1.47 78 microcrystalline 5.50 II-12 3.74 80microcrystalline 5.48 II-13 0.71 80 microcrystalline 5.47 II-14 1.56 76microcrystalline 5.46 II-15 2.65 78 microcrystalline 5.47 II-16 0.65 78amorphous 5.54 II-17 2.56 74 amorphous 5.48 II-18 3.62 76 amorphous 5.49II-19 0.72 79 amorphous 5.55 II-20 1.27 76 amorphous 5.50 Example(Comparative Example) II-21 4.27 75 amorphous 5.51 II-22 1.40 80amorphous 5.53 II-23 0.71 81 crystalline 5.52 II-24 0.84 80 amorphous5.51 II-25 1.70 78 amorphous 5.51 (II-1) 0.34 80 amorphous 5.18 (II-2)0.18 82 crystalline 4.97

[Third Aspect of the Invention]

EXAMPLE III-1

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, tin oxide and iridium oxide werefed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.90

Zn/(In+Zn+Sn)=0.00

Sn/(In+Zn+Sn)=0.10, and

Ir/(In+Zn+Sn+Ir)=0.04,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

The powdery, transparent electroconductive material obtained in (1) wasgranulated, and then pressed into discs having a diameter of 4 inchesand a thickness of 5 mm. The discs were put into a baking furnace andbaked therein under pressure at 1400° C. for 36 hours.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of0.98 mΩ·cm.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

The sintered product having been prepared in (2) was formed intosputtering targets having a diameter of 4 inches and a thickness of 5mm. The target was set in a DC magnetron sputtering unit, and sputteredonto a glass substrate set therein.

Regarding the sputtering condition, the atmosphere in the unit was argongas combined with a suitable amount of oxygen gas; the sputteringpressure was 3×10⁻¹ Pa; the ultimate vacuum degree was 5×10⁻⁴ Pa; thesubstrate temperature was 25° C.; the power applied was 80 W; the timefor film deposition was 14 minutes.

The transparent electroconductive film formed on the glass substrate hada thickness of 1,200 angstroms, and was amorphous. Its lighttransmittance for light having a wavelength of 500 nm was measured witha spectrophotometer, and was 81%. The specific resistance of the film,measured according to a 4-probe method, was 1.2 mΩ·cm, and theelectroconductivity of the film was high. The work function of the filmwas measured through UV photoelectron spectrometry, and was 5.46electron volts.

The physical properties of the transparent electroconductive film aregiven in Table III-2.

EXAMPLE III-2

(1) Production of Transparent Electroconductive Glass

The same sputtering target as in Example III-1 was used, and transparentelectroconductive glass was produced in the same manner as in the step(3) in Example III-1. In this, however, the substrate temperature was215° C.

The physical properties of the transparent electroconductive film formedon the glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-3

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, tin oxide and iridium oxide werefed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.70

Zn/(In+Zn+Sn)=0.00

Sn/(In+Zn+Sn)=0.30, and

Ir/(In+Zn+Sn+Ir)=0.08,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-4

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, tin oxide and iridium oxide werefed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.25

Zn/(In+Zn+Sn)=0.00

Sn/(In+Zn+Sn)=0.75, and

Ir/(In+Zn+Sn+Ir)=0.05,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powder, transparent electroconductive material obtained in (1),produced were sintered discs in the same manner as in the step (2) inExample III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-5

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide and iridium oxide were fed into awet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=1.00

Zn/(In+Zn+Sn)=0.00

Sn/(In+Zn+Sn)=0.00, and

Ir/(In+Zn+Sn+Ir)=0.04,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-6

(1) Production of Transparent Electroconductive Material

Raw material powders of zinc oxide, tin oxide and iridium oxide were fedinto a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.00

Zn/(In+Zn+Sn)=0.20

Sn/(In+Zn+Sn)=0.80, and

Ir/(In+Zn+Sn+Ir)=0.05,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was: thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-7

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, zinc oxide, tin oxide and iridiumoxide were fed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.80

Zn/(In+Zn+Sn)=0.10

Sn/(In+Zn+Sn)=0.10, and

Ir/(In+Zn+Sn+Ir)=0.06,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-8

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, zinc oxide, tin oxide and iridiumoxide were fed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.05

Zn/(In+Zn+Sn)=0.90

Sn/(In+Zn+Sn)=0.05, and

Ir/(In+Zn+Sn+Ir)=0.06,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-9

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, zinc oxide and iridium oxide werefed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.85

Zn/(In+Zn+Sn)=0.15

Sn/(In+Zn+Sn)=0.00, and

Ir/(In+Zn+Sn+Ir)=0.06,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powder, transparent electroconductive material obtained in (1),produced were sintered discs in the same manner as in the step (2) inExample III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-10

(1) Production of Transparent Electroconductive Glass

The same sputtering target as in Example III-9 was used, and transparentelectroconductive glass was produced in the same manner as in the step(3) in Example III-1. In this, however, the substrate temperature was215° C.

The physical properties of the transparent electroconductive film formedon the glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-11

(1) Production of Transparent Electroconductive Film

The same sputtering target as in Example III-10 was used, and atransparent electroconductive film was produced in the same manner as inthe step (3) in Example III-1. In this, however, a transparent resinfilm of polycarbonate was used as the substrate in place of the glasssubstrate.

The physical properties of the transparent electroconductive film formedon the resin substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-12

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, tin oxide and rhenium oxide werefed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.90

Zn/(In+Zn+Sn)=0.00

Sn/(In+Zn+Sn)=0.10, and

Re/(In+Zn+Sn+Re)=0.04,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-13

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, zinc oxide and rhenium oxide werefed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.85

Zn/(In+Zn+Sn)=0.15

Sn/(In+Zn+Sn)=0.00, and

Re/(In+Zn+Sn+Re)=0.06,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-14

(1) Production of Transparent Electroconductive Film

The same sputtering target as in Example III-13 was used, and atransparent electroconductive film was produced in the same manner as inthe step (3) in Example III-1. In this, however, a transparent resinfilm of polycarbonate was used as the substrate in place of the glasssubstrate.

The physical properties of the transparent electroconductive film formedon the resin substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-15

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, zinc oxide, tin oxide and rheniumoxide were fed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.80

Zn/(In+Zn+Sn)=0.10

Sn/(In+Zn+Sn)=0.10, and

Re/(In+Zn+Sn+Re)=0.05,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

EXAMPLE III-16

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide, zinc oxide and palladium oxidewere fed into a wet ball mill in the following atomic ratios:

In/(In+Zn+Sn)=0.80

Zn/(In+Zn+Sn)=0.20

Sn/(In+Zn+Sn)=0.00, and

Pd/(In+Zn+Sn+Pd)=0.05,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table III-1.

(2) Production of Sintered Discs

From the powdery, transparent electroconductive material obtained in(1), produced were sintered discs in the same manner as in the step (2)in Example III-1.

The physical properties of the sintered discs were measured, and thedata are given in Table III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in Table1II-2.

Comparative Example III-1

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide and zinc oxide were fed into a wetball mill in the following atomic ratios:

In/(In+Zn)=0.85

Zn/(In+Zn)=0.15,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

(2) Production of Sintered Discs

From the transparent electroconductive material obtained in (1),produced were sintered discs in the same manner as in the step (2) inExample III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2). Thephysical properties of the transparent electroconductive film formed onthe glass substrate were measured, and the data are given in TableIII-2.

Comparative Example III-2

(1) Production of Transparent Electroconductive Material

Raw material powders of indium oxide and tin oxide were fed into a wetball mill in the following atomic ratios:

In/(In+Sn)=0.90

Sn/(In+Sn)=0.10,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

(2) Production of Sintered Discs

From the transparent electroconductive material obtained in (1),produced were sintered discs in the same manner as in the step (2) inExample III-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example III-1. In this, however, used was thesintered product that had been prepared in the previous step (2), andthe glass substrate temperature was 215° C. The physical properties ofthe transparent electroconductive film formed on the glass substratewere measured, and the data are given in Table III-2.

TABLE III-1 Example III-1 III-3 III-4 III-5 III-6 III-7 III-8 In/(In +Zn + Sn) 0.90 0.70 0.25 1.0 — 0.80 0.05 Zn/(In + Zn + Sn) — — — — 0.200.10 0.90 Sn/(In + Zn + Sn) 0.10 0.30 0.75 — 0.90 0.10 0.05 Ir/(In +Zn + Sn + Ir) 0.04 0.08 0.05 0.04 0.05 0.06 0.06 Re/(In + Zn + Sn + Re)— — — — — — — Pd/(In + Zn + Sn + Pd) — — — — — — — Density of SinteredDiscs (g/cm³) 6.8 6.6 6.3 6.7 6.2 6.9 5.8 Bulk Resistance (mΩ · cm) 0.981.4 4.7 0.92 8.9 0.95 9.9 Example (Comparative Example) III-9 III-11III-12 III-13 III-16 (III-1) (III-2) In/(In + Zn + Sn) 0.85 0.90 0.850.80 0.90 0.85 0.90 Zn/(In + Zn + Sn) 0.15 — 0.15 0.10 0.20 0.15 —Sn/(In + Zn + Sn) — 0.10 — 0.10 — — 0.10 Ir/(In + Zn + Sn + Ir) 0.06 — —— — — — Re/(In + Zn + Sn + Re) — 0.04 0.06 0.05 — — — Pd/(In + Zn + Sn +Pd) — — — — 0.05 — — Density of Sintered Discs (g/cm³) 6.8 6.7 6.8 6.36.48 6.9 6.71 Bulk Resistance (mΩ · cm) 1.0 0.85 0.94 0.73 3.4 2.4 0.69

TABLE III-2 Specific Substrate Resistance of Film Light Temperature (°C.) (mΩ · cm) Transmittance (%) Crystallinity Work Function (eV) ExampleIII-1  25 1.2 81 amorphous 5.46 III-2  215 0.52 82 microcrystalline 5.45III-3  25 1.7 82 amorphous 5.47 III-4  25 3.8 81 amorphous 5.48 III-5 25 0.80 80 amorphous 5.45 III-6  25 450 80 amorphous 5.46 III-7  25 1.181 amorphous 5.54 III-8  25 8.8 78 amorphous 5.48 III-9  25 1.3 82amorphous 5.54 Example (Comparative Example) III-10 215 0.56 80amorphous 5.49 III-11 25 0.45 82 amorphous 5.45 III-12 25 0.64 81amorphous 5.48 III-13 25 0.55 82 amorphous 5.47 III-14 25 1.3 82amorphous 5.54 III-15 25 0.64 81 amorphous 5.48 III-16 25 360 76amorphous 5.61 (III-1) 25 0.32 80 amorphous 5.18 (III-2) 215 0.18 82crystalline 4.95

[Fourth Aspect of the Invention]

EXAMPLE IV-1

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders of tin oxide, zinc oxide and vanadium oxide werefed into a wet ball mill in the following atomic ratios:

Sn/(Sn+In+Zn)=0.80

In/(Sn+In+Zn)=0.00

Zn/(Sn+In+Zn)=0.20, and

V/(Sn+In+Zn+V)=0.04,

and mixed and ground therein for 72 hours to prepare powder of atransparent electroconductive material.

The atomic ratio of the metal atoms constituting the transparentelectroconductive material obtained herein is given in Table IV-1.

(2) Production of Sintered Discs

The powdery, transparent electroconductive material obtained in (1) wasgranulated, and then pressed into discs having a diameter of 4 inchesand a thickness of 5 mm. The discs were put into a baking furnace andbaked therein under pressure at 1400° C. for 36 hours.

The sintered discs had a density of 6.8 g/cm³ and a bulk resistance of6.5 mΩ·cm.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

The sintered product having been prepared in (1) was formed intosputtering targets [A] having a diameter of 4 inches and a thickness of5 mm. The target was set in a DC magnetron sputtering unit, andsputtered onto a glass substrate set therein.

Regarding the sputtering condition, the atmosphere in the unit was argongas combined with a suitable amount of oxygen gas; the sputteringpressure was 3×10⁻¹ Pa; the ultimate vacuum degree was 5×10⁻⁴ Pa; thesubstrate temperature was 25° C.; the power applied was 100 W; the timefor film deposition was 14 minutes.

The transparent electroconductive film formed on the glass substrate hada thickness of 1,200 angstroms, and was amorphous. Its lighttransmittance for light having a wavelength of 500 nm was measured witha spectrophotometer, and was 80%. The specific resistance of the film,measured according to a 4-probe method, was 1,000 mΩ·cm. The workfunction of the film was measured through UV photoelectron spectrometry,and was 5.50 electron volts.

The physical properties of the transparent electroconductive film aregiven in Table IV-2.

EXAMPLE IV-2

Using the same sputtering target [A] as in Example IV-1, transparentelectroconductive glass was produced in the same manner as in the step(3) in Example IV-l except for the sputtering condition. In this, thesubstrate temperature was 215° C.

The physical properties of the transparent electroconductive film formedon the glass substrate are given in Table IV-2.

EXAMPLE IV-3

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, zinc oxide and vanadium oxide were mixed inthe atomic ratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [B]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

EXAMPLE IV-4

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, zinc oxide and vanadium oxide were mixed inthe atomic ratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [C]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

EXAMPLE IV-5

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide and vanadium oxide were mixed inthe atomic ratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [D]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

EXAMPLE IV-6

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide and vanadium oxide were mixed in the atomicratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [E]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

EXAMPLE IV-7

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide, zinc oxide and vanadium oxidewere mixed in the atomic ratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [F]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

EXAMPLE IV-8

(1) Production of Transparent Electroconductive Film

Using a transparent polycarbonate film but not glass as the substrateand using the sputtering target [F] that had been prepared in ExampleIV-7, a transparent electroconductive film was produced.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

EXAMPLE IV-9

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide, zinc oxide and vanadium oxidewere mixed in the atomic ratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [G]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

Comparative Example IV-1

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of indium oxide and zinc oxide were mixed in the atomicratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [H]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

Comparative Example IV-2

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide and indium oxide were mixed in the atomicratios indicated in Table IV-1.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

At The physical properties of the sintered discs were measured, and thedata are given in Table IV-1.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [I]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

Comparative Example IV-3

(1) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1. In this, however, the sputtering target[H] that had been prepared in Comparative Example IV-1 was used, and thetemperature of the glass substrate in the sputtering step was 215° C.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

Comparative Example IV-4

(1) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1. In this, however, the sputtering target[I] that had been prepared in Comparative Example IV-2 was used, and thetemperature of the glass substrate in the sputtering step was 215° C.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-2.

TABLE IV-1 Example (Comparative Example) IV-1 IV-3 IV-4 IV-5 IV-6 IV-7IV-9 (IV-1) (IV-2) Sn/(Sn + In + Zn) 0.60 0.95 0.55 0.60 1.00 0.60 0.60— 0.10 In/(Sn + In + Zn) — — 0.45 0.20 — 0.10 0.15 0.65 0.90 Zn/(Sn +In + Zn) 0.20 0.05 — — — 0.10 0.05 0.15 — V/(Sn + In + Zn + V) 0.040.032 0.035 0.03 0.02 0.05 0.035 — — Density of Sintered 6.6 6.6 6.5 6.66.5 6.7 6.6 6.75 6.71 Discs (g/cm³) Bulk Resistance 6.5 5.6 6.3 6.6 6.13.6 4.2 2.74 0.69 (mΩ · cm) Target Code [A] [B] [C] [D] [E] [F] [G] [H][I]

TABLE IV-2 Example Substrate Specific Light (Comparative TemperatureResistance of Transmittance Work Function Example) Target Code (° C.)Film (mΩ · cm) (%) Crystallinity (eV) IV-1 [A] 25 1000 80 amorphous 5.50IV-2 [A] 215 1000 81 crystalline 5.51 IV-3 [B] 25 700 80 amorphous 5.49IV-4 [C] 25 3 81 amorphous 5.48 IV-5 [D] 25 5 80 amorphous 5.47 IV-8 [E]25 4 81 amorphous 5.46 IV-7 [F] 25 1 82 amorphous 5.48 IV-8 [F] 25 1 82amorphous 5.48 IV-9 [G] 25 2 81 amorphous 5.48 (IV-1) [H] 25 0.34 80amorphous 5.16 (IV-2) [I] 25 0.42 80 microcrystalline 4.97 (IV-3) [H]215 0.32 80 amorphous 5.18 (IV-4) [I] 215 0.18 82 crystalline 4.95

EXAMPLE IV-10

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, zinc oxide and molybdenum oxide were mixed inthe atomic ratios indicated in Table IV-3.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-3.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [J]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

EXAMPLE IV-11

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, zinc oxide:and molybdenum oxide were mixed inthe atomic ratios indicated in Table IV-3.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-3.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [K]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

EXAMPLE IV-12

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide and molybdenum oxide were mixedin the atomic ratios indicated in Table IV-3.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-3.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [L]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

EXAMPLE IV-13

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide, zinc oxide and molybdenum oxidewere mixed in the atomic ratios indicated in Table IV-3.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-3.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [M]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

EXAMPLE IV-14

(1) Production of Transparent Electroconductive Glass

Using the sputtering target [M] that had been prepared in Example IV-13,transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1. In this, however, the glass substratetemperature was 215° C.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

EXAMPLE IV-15

(1) Production of Transparent Electroconductive Film

Using a transparent polycarbonate film but not glass as the substrateand using the sputtering target [M] that had been prepared in ExampleIV-13, a transparent electroconductive film was produced in the samemanner as in the step (3) in Example IV-1.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

EXAMPLE IV-16

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide, zinc oxide and molybdenum oxidewere mixed in the atomic ratios indicated in Table IV-3.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-3.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [N]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-4.

TABLE IV-3 Example IV-10 IV-11 IV-12 IV-13 IV-16 Sn/(Sn + In + Zn) 0.800.95 0.80 0.80 0.80 In/(Sn + In + Zn) — — 0.20 0.10 0.15 Zn/(Sn + In +Zn) 0.20 0.05 — 0.10 0.05 Mo/(Sn + In + Zn + Mo) 0.04 0.032 0.03 0.050.04 Density of Sintered Discs (g/cm³) 6.7 6.5 6.7 6.8 6.7 BulkResistance (mΩ · cm) 5.3 4.9 5.2 3.6 3.8 Target Code [J] [K] [L] [M] [N]

TABLE IV-4 Substrate Specific Light Temperature Resistance ofTransmittance Work Function Example Target Code (° C.) Film (mΩ · cm)(%) Crystallinity (eV) IV-10 [J] 25 850 80 amorphous 5.47 IV-11 [K] 25650 81 crystalline 5.49 IV-12 [L] 25 8 80 amorphous 5.49 IV-13 [M] 25 181 amorphous 5.48 IV-14 [M] 215 0.8 80 amorphous 5.47 IV-15 [M] 25 1 81amorphous 5.48 IV-16 [N] 25 2 81 amorphous 5.46

EXAMPLE IV-17

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, zinc oxide and ruthenium oxide were mixed inthe atomic ratios indicated in Table IV-5.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared. in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-5.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin, the step (3) in Example IV-1, except that the sputtering target [O]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

EXAMPLE IV-18

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, zinc oxide and ruthenium oxide were mixed inthe atomic ratios indicated in Table IV-5.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-5.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [P]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

EXAMPLE IV-19

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide and ruthenium oxide were mixedin the atomic ratios indicated in Table IV-5.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-5.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [Q]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

EXAMPLE IV-20

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide, zinc oxide and ruthenium oxidewere mixed in the atomic ratios indicated in Table IV-5.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-5.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [R]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

EXAMPLE IV-21

(1) Production of Transparent Electroconductive Glass

Using the sputtering target [R] that had been prepared in Example IV-20,transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1. In this, however, the glass substratetemperature was 215° C.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

EXAMPLE IV-22

(1) Production of Transparent Electroconductive Film

Using a transparent polycarbonate film but not glass as the substrateand using the sputtering target [R] that had been prepared in ExampleIV-20, a transparent electroconductive film was produced in the samemanner as in the step (3) in Example IV-1.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

EXAMPLE IV-23

(1) Production of Raw Material Powders for Transparent ElectroconductiveMaterial

Raw material powders for a transparent electroconductive material wereprepared in the same manner as in the step (1) in Example IV-1, exceptthat powders of tin oxide, indium oxide, zinc oxide and ruthenium oxidewere mixed in the atomic ratios indicated in Table IV-5.

(2) Production of Sintered Discs

Sintered discs were produced in the same manner as in the step (2) inExample IV-1, except that the powdery, transparent electroconductivematerial having been prepared in the previous (1) was used herein.

The physical properties of the sintered discs were measured, and thedata are given in Table IV-5.

(3) Production of Transparent Electroconductive Glass

Transparent electroconductive glass was produced in the same manner asin the step (3) in Example IV-1, except that the sputtering target [S]of the sintered product having been prepared in the previous (2) wasused herein.

The physical properties of the transparent electroconductive film formedherein are given in Table IV-6.

TABLE IV-5 Example IV-17 IV-18 IV-19 IV-20 IV-23 Sn/(Sn + In + Zn) 0.800.95 0.80 0.80 0.80 In/(Sn + In + Zn) — — 0.20 0.10 0.15 Zn/(Sn + In +Zn) 0.20 0.05 — 0.10 0.05 Ru/(Sn + In + Zn + Ru) 0.04 0.032 0.03 0.050.04 Density of Sintered Discs (g/cm³) 6.5 6.4 6.6 6.7 6.7 BulkResistance (mΩ · cm) 4.2 5.6 4.25 3.4 3.6 Target Code [O] [P] [Q] [R][S]

TABLE IV-6 Substrate Specific Light Temperature Resistance ofTransmittance Work Function Example Target Code (° C.) Film (mΩ · cm)(%) Crystallinity (eV) IV-17 [O] 25 45 81 amorphous 5.51 IV-18 [P] 25 4282 crystalline 5.48 IV-19 [Q] 25 6 81 amorphous 5.47 IV-20 [R] 25 2 80amorphous 5.52 IV-21 [R] 215 1 82 amorphous 5.49 IV-22 [R] 25 2 80amorphous 5.52 IV-23 [S] 25 2 81 amorphous 5.51

INDUSTRIAL APPLICABILITY

As described hereinabove, the invention provides sintered products forTransparent electroconductive films, which are formed into films in astable and efficient manner through sputtering or the like, sputteringtargets of the sintered products, and transparent electroconductiveglass and films formed from the targets. The transparentelectroconductive glass and films have good transparency, goodelectroconductivity and good workability into electrodes, and aretherefore favorable to transparent electrodes in organicelectroluminescent devices as realizing good hole injection efficiencytherein.

What is claimed is:
 1. A sintered product that comprises constituentcomponents of indium oxide, tin oxide and zinc oxide in the followingatomic ratios: In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.25 to 0.45,Zn/(In+Sn+Zn)=0.03 to 0.30, and contains a hexagonal layer compound ofIn₂O₃.(ZnO)m with m indicating an integer of from 2 to 20, and aspinel-structured compound of Zn₂SnO₄.
 2. The sintered product asclaimed in claim 1, which has a specific resistance of smaller than 2mΩ·cm.
 3. A sintered product that comprises constituent components ofindium oxide, tin oxide and zinc oxide in the following atomic ratios:In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.25 to 0.45,Zn/(In+Sn+Zn)=0.03 to 0.30, and from 0.5 to 10 atomic %, relative to thetotal of all metal atoms therein, of an oxide of a positive tetra-valentor higher poly-valent metal, and contains a hexagonal layer compound ofIn₂O₃.(ZnO)m with m indicating an integer of from 2 to 20, and aspinel-structured compound of Zn₂SnO₄.
 4. The sintered product asclaimed in claim 3, in which the oxide of a positive tetra-valent orhigher poly-valent metal is ruthenium oxide, molybdenum oxide orvanadium oxide.
 5. A sputtering target for transparent electroconductivefilms, which comprises the sintered product of claim
 1. 6. Anelectron-beaming target for transparent electroconductive films, whichcomprises the sintered product of claim
 1. 7. An ion-plating target fortransparent electroconductive films, which comprises the sinteredproduct of claim
 1. 8. Transparent electroconductive glass prepared bycoating the surface of glass with an amorphous transparentelectroconductive film that comprises constituent components of indiumoxide, tin oxide and zinc oxide in the following atomic ratios:In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.25 to 0.45,Zn/(In+Sn+Zn)=0.03 to 0.30, and contains from 0.5 to 10 atomic %,relative to the total of all metal atoms therein, of an oxide of apositive tetra-valent or higher poly-valent metal.
 9. The transparentelectroconductive glass as claimed in claim 8, in which the oxide of apositive tetra-valent or higher poly-valent metal is ruthenium oxide,molybdenum oxide or vanadium oxide.
 10. The transparentelectroconductive glass as claimed in claim 8, which has a lighttransmittance of at least 75% and a specific resistance of at most 5mΩ·cm, and in which the transparent electroconductive film has a workfunction of at least 5.45.
 11. A transparent electroconductive filmprepared by coating the surface of a transparent resin film with anamorphous transparent electroconductive layer that comprises constituentcomponents of indium oxide, tin oxide and zinc oxide in the followingatomic ratios: In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.25 to 0.45,Zn/(In+Sn+Zn)=0.03 to 0.30, and contains from 0.5 to 10 atomic %,relative to the total of all metal atoms therein, of an oxide of apositive tetra-valent or higher poly-valent metal.
 12. The transparentelectroconductive film as claimed in claim 11, in which the oxide of apositive tetra-valent or higher poly-valent metal is ruthenium oxide,molybdenum oxide or vanadium oxide.
 13. The transparentelectroconductive film as claimed in claim 11, which has a lighttransmittance of at least 75% and a specific resistance of at most 5mΩ·cm, and in which the transparent electroconductive layer has a workfunction of at least 5.45.